Interfacial Effects in ε-LixVOPO4 and Evolution of the Electronic Structure

Quackenbush, N. F.; Wangoh, L.; Scanlon, D. O.; Zhang, R.; Chung, Y.; Chen, Z.; Wen, B.; Lin, Y.; Woicik, J. C.; Chernova, N. A.; Ong, S. P.; Whittingham, M. S.; Piper, L. F.  J.

doi:10.1021/acs.chemmater.5b02145

Interfacial Effects in ε-Li_xVOPO₄ and Evolution of the Electronic Structure

Journal Article · Tue Dec 08 19:00:00 EST 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b02145· OSTI ID:1387345

Quackenbush, N. F. ^[1]; Wangoh, L. ^[1]; Scanlon, D. O. ^[2]; Zhang, R. ^[1]; Chung, Y. ^[3]; Chen, Z. ^[4]; Wen, B. ^[5]; Lin, Y. ^[6]; Woicik, J. C. ^[7]; Chernova, N. A. ^[1]; Ong, S. P. ^[6]; Whittingham, M. S. ^[3]; Piper, L. F. J. ^[1]

Binghamton Univ., NY (United States)
Univ. College London, London (United Kingdom)
State Univ. of New York (SUNY), Binghamton, NY (United States). The Northeast Center for Chemical Energy Storage (NECCES)
Central South Univ., Changsha (China); State Univ. of New York (SUNY), Binghamton, NY (United States)
State Univ. of New York (SUNY), Binghamton, NY (United States)
Univ. of California, San Diego, CA (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

The epsilon polymorph of vanadyl phosphate ε-VOPO₄ is a promising cathode material for high-capacity Li ion batteries, owing to its demonstrated ability to reversibly incorporate two lithium ions per redox center. As lithium is inserted into the nanosized particles within the cathode, the electrochemical reaction can be largely affected by the interfacial chemistry at the nanoparticle surface. We performed X-ray photoelectron spectroscopy using both soft (XPS) and hard (HAXPES) X-rays to chemically distinguish and depth-resolve the interfacial phase transitions in ε-VOPO₄ electrodes as a function of electrochemical discharge. Our analysis shows that the second lithium reaction begins before the full incorporation of the first lithium. This results in a pronounced lithium gradient within the nanoparticles, with the ε-Li₂VOPO₄ phase only forming near the surface. These results indicate that a disruption of the kinetics are limiting the realized capacity in our hydrothermally synthesized ε-VOPO₄. Moreover, from inspection of the valence band region, we were able to monitor the evolution of ε-VOPO₄ to ε-Li2VOPO₄ at the surface of our nanoparticles. These assignments are confirmed by hybrid density functional theory of the three end phases.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001294; SC0012583; AC02-98CH10886

OSTI ID:: 1387345

Alternate ID(s):: OSTI ID: 1354408

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 24 Vol. 27; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Electrochemical Performance of Nanosized Disordered LiVOPO ₄ Shi, Yong; Zhou, Hui; Seymour, Ieuan D. ACS Omega, Vol. 3, Issue 7 https://doi.org/10.1021/acsomega.8b00763	journal	July 2018
Delithiation/lithiation behaviors of three polymorphs of LiVOPO ₄ He, Guang; Kan, Wang Hay; Manthiram, Arumugam Chemical Communications, Vol. 54, Issue 94 https://doi.org/10.1039/c8cc07446a	journal	January 2018
Role of disorder in limiting the true multi-electron redox in ε-LiVOPO ₄ Rana, Jatinkumar; Shi, Yong; Zuba, Mateusz J. Journal of Materials Chemistry A, Vol. 6, Issue 42 https://doi.org/10.1039/c8ta06469e	journal	January 2018
A Two-Color Beamline for Electron Spectroscopies at Diamond Light Source Lee, Tien-Lin; Duncan, David A. Synchrotron Radiation News, Vol. 31, Issue 4 https://doi.org/10.1080/08940886.2018.1483653	journal	July 2018
Evaluation of α ₁ -LiVOPO ₄ , β-LiVOPO ₄ , and α-LiVOPO ₄ Synthesized from a Same Precursor by Hydrothermal Method Nojima, Akinobu; Sano, Atsushi; Fujita, Shin Journal of The Electrochemical Society, Vol. 166, Issue 15 https://doi.org/10.1149/2.0691915jes	journal	January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
charge transport
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